Patent GB-450700-A (GB)
Title: Manufacture of dyestuffs of the anthraquinone series
IPC: C09B3/72
Filed: 1935-02-27
Abstract: Heterocyclic members of the dianthraquinonyl-series and the dianthrone series are prepared by treating a dianthraquinonyl compound of the formula <FORM:0450700/IV/1> wherein X stands for NH2 or an acylamino group and Z for hydrogen or a methyl group, and wherein the carbon atoms in the 9,9<1>-positions or in the 9,9<1>- and 8,8<1>-positions can be directly connected, with acid or alkaline condensing agents, if desired after treatment with a reducing agent, and, if necessary, subsequent oxidation, in such a manner that, both 2-positions are united by a bridge containing nitrogen, and, if desired, the product is halogenated.  In the case where a 2-acylamino derivative is used as starting-material, saponification is effected before or during the condensation. The products belong to the dianthraquinonyl, benzdianthrone or naphthodianthrone series also containing a carbazole or phenanthridine structure.  In examples: (1) 2-amino-1.1<1>-dianthraquinonyl (prepared by treating with copper in a high-boiling solvent a mixture of 1-halogen-2-acylaminoanthraquinone and 1-halogenanthraquinone and saponifying) is treated with sodium-aluminium chloride at 150 DEG  C. to give a carbazole dyeing olive shades; (2) 2-phthalimino-1.1<1>-dianthraquinonyl (prepared by treating a mixture of 1-halogen-2-phthaliminoanthraquinone and 1 - halogenanthraquinone with copper in a high-boiling solvent) is treated with copper in sulphuric acid to give 2 - phthalimino-ms - benzdianthrone, which is saponified by treatment with hydrazine in pyridine and ring-closed by means of alcoholic caustic potash to 2.2<1>-imino-ms-benzdianthrone (red-brown shades); 2-phthalimino-2<1>-methyl-1.1<1>-dianthraquinonyl (similarly derived) is converted by these operations to allopyridino-ms-benzdianthrone (salmon-red); (3) 2-phthalimino - 2<1> - methyl - ms - benzdianthrone (cf. example 2) is treated with manganese dioxide in strong sulphuric acid and the resulting naphthodianthrone saponified and ring-closed as in (2) to give allo-pyridino-ms-naphthodianthrone (orange shades); (4) allo-pyridino-ms-benzdianthrone (cf. example 2) is treated with sulphuryl chloride in nitrobenzene (red) and with bromine in chlorsulphonic acid (redbrown); (5) 2-amino-ms-benzdianthrone is ring-closed by means of sodium-aluminium chloride to 2.2<1>-imino-ms-naphthodianthrone.  A further example illustrates the application of the products to cotton.  The Specification as open to inspection under Sect. 91 relates to a treatment as above applied to compounds of the foregoing formula wherein x stands for NH2 or a group convertible to an amino group by saponification and z stands for hydrogen or a group which can take part in forming a ring, for instance, a methyl or amino group.  In examples, reference is made to the production of 2.2<1> - diphthalimino - ms - benzdianthrone from 2.2<1>-diphthalimino-1.1<1>-dianthraquinonyl by treatment p  with copper in sulphuric acid and saponification of this by means of hydrazine; to the oxidation of 2-phthalimino-ms-benzdianthrone with manganese dioxide and sulphuric acid to the corresponding naphthodianthrone; and to the oxidation of the chlorinated product of example 4 above.  This subject-matter does not appear in the Specification as accepted.